Syntheses, third-order optical nonlinearity and DFT studies on benzoylferrocene derivatives

Article abstract of DOI:10.1016/j.dyepig.2014.01.006

A series of benzoylferrocene derivatives were synthesized and their third-order nonlinear optical (NLO) properties were evaluated in N,N-dimethyl-formamide at 800 nm using femtosecond degenerate four-wave mixing. The third-order NLO susceptibilities of synthesized compounds were 3.065-7.859 × 10^-13 esu, with the response times in 49-70 fs. The second-order hyperpolarizabilities of the molecules of the compounds were 1.018-2.611 × 10^-31 esu. The Density Functional Theory was used to calculate these benzoylferrocene derivatives. The theoretical study showed that the third-order NLO properties were increased with the increasing electron-withdrawing ability, which is accordance with the decreasing energy gap between the highest occupied and the lowest unoccupied molecular orbital. With the increasing of electron-withdrawing ability, the transferred charge to the substituent was increased and the affection on the electronic reallocate was increased. The experiment and theoretical results showed that the benzoylferrocene derivatives had potential nonlinear optical applications.

Full text of DOI:10.1016/j.dyepig.2014.01.006

Dyes and Pigments 104 (2014) 137e145
Contents lists available at ScienceDirect
Dyes and Pigments
journal homepage: www.elsevier.com/locate/dyepig
Syntheses, third-order optical nonlinearity and DFT studies on
benzoylferrocene derivatives
*
Jianhong Jia, Yanhong Cui, Liang Han, Weijian Sheng, Yujin Li, Jianrong Gao
College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310032, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
A series of benzoylferrocene derivatives were synthesized and their third-order nonlinear optical (NLO)
properties were evaluated in N,N-dimethyl-formamide at 800 nm using femtosecond degenerate four-
wave mixing. The third-order NLO susceptibilities of synthesized compounds were 3.065e7.859 ꢀ 10
ꢁ13 esu, with the response times in 49e70 fs. The second-order hyperpolarizabilities of the molecules of
the compounds were 1.018e2.611 ꢀ 10ꢁ31 esu. The Density Functional Theory was used to calculate these
benzoylferrocene derivatives. The theoretical study showed that the third-order NLO properties were
increased with the increasing electron-withdrawing ability, which is accordance with the decreasing
energy gap between the highest occupied and the lowest unoccupied molecular orbital. With the
increasing of electron-withdrawing ability, the transferred charge to the substituent was increased and
the affection on the electronic reallocate was increased. The experiment and theoretical results showed
that the benzoylferrocene derivatives had potential nonlinear optical applications.
Received 20 October 2013
Received in revised form
23 December 2013
Accepted 3 January 2014
Available online 13 January 2014
Keywords:
Benzoylferrocene derivatives
Nonlinear optics
DFWM technique
The third-order NLO
Functional dyes
Crown Copyright Ó 2014 Published by Elsevier Ltd. All rights reserved.
Density Functional Theory
1. Introduction
properties, good thermal and photochemical stability, and redox
switching abilities have caused considerable interests.
Design and synthesis of the excellent performance of the three
order nonlinear optical (NLO) materials is a hot research topic in
recent years [1]. Organic materials had been investigated as alter-
natives to inorganic species due to their low cost, fast and large
nonlinear response over a broad frequency range, inherent syn-
thetic flexibility, low dielectric constant, high optical-damage
threshold, and intrinsic tailorability [2,3]. Nonlinear optical
response of organic materials comes from the molecular polariz-
Ferrocene, with its unique electrical, magnetic, optical, redox,
and crystal properties, as well as its high thermal and chemical
stability, is a very useful building block in the construction of
various functional materials and has been used in numerous me-
dicinal and bioorganometallic chemistry applications [14e16]. In
this context, we have been involved in the study of NLO properties
of ferrocene derivatives. We had previously reported that ferro-
cene, as an electron donor and/or an acceptor was an excellent
building block for the construction of organic NLO materials [17e
21]. These studies had focused on the important role of ferrocene
substituents enhancing third-order NLO properties of such mate-
rials. In addition, most process for synthesis of benzoylferrocene
derivatives require extremely low temperature (ꢁ78 ꢂC) [22],
strong corrosive reagent (triflic acid) [23], or abnormal reagent [24].
In the present work we found a simple and efficient method for the
synthesis of benzoylferrocene derivatives (Fig. 1). The third-order
NLO properties of these materials had been measured and
compared with the data calculated by the Density Functional
Theory (DFT) of quantum chemistry. The NLO properties were
illustrated well with the energy of the highest occupied molecular
orbital (HOMO), the energy of the lowest unoccupied molecular
orbital (LOMO), the HOMO and LUMO gap (Egap), the natural charge,
and MOs. This is the first study on the NLO properties for
ability of nonlocalized
different from inorganic materials. Because the movement of
nonlocalized -electron is easy and not affected by lattice vibra-
p-electron under the light field, which is
p
tions, the NLO response of organic materials are stronger and faster
than that of inorganic materials [4]. To date, many kinds of organic
NLO materials have been synthesized, such as DeA pushepull
structure of azo compounds [5,6], squaric acid [7], heterocyclic
compounds [8,9], tetrathiafulvalene derivatives [10], schiff base
complex [11], metal phthalocyanine compounds [12], and ferrocene
derivatives [13]. Among them, metal complexes with potential NLO
* Corresponding author.
E-mail address: zjutgjr@163.com (J. Gao).
0143-7208/$ e see front matter Crown Copyright Ó 2014 Published by Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.dyepig.2014.01.006

138
J. Jia et al. / Dyes and Pigments 104 (2014) 137e145
Fig. 1. Synthetic routes of benzoylferrocene derivatives.
benzoylferrocene derivatives by experiments combined with
quantum chemistry.
Ferrocene (1.86 g, 10.0 mmol) was combined with chloroform
(50.0 mL) and stirred at 0e5 ꢂC. Afterward, the above crude benzoyl
chloride derivatives was dissolved in 15.0 mL chloroform and
added slowly. Anhydrous aluminum chloride (8.0 g, 60.0 mmol)
was added in batches. The mixture was warmed to room temper-
ature for at least 1.0 h. The reaction was quenched with the ice
water (100 mL), and then the mixture was shaken, standing and
demixed. The organic layer was evaporated to dryness by rotary
evaporation after washing with alkali and water. The residue was
purified by chromatography on silica gel to afford benzoylferrocene
derivatives 3.
2. Experimental section
2.1. Materials
Unless otherwise stated, starting materials were used as pur-
chased without further purification. The dimethylformamide
(DMF) was distilled from CaH2.
2.2. Instruments
2.3.2. Benzoylferrocene (3a)
Red powder; yield 64.9%, m.p. 109e110 ꢂC. 1H NMR (500 MHz,
The 1H nuclear magnetic-resonance (1H MNR) spectra were
obtained on a Varian XL-200 spectrometer. Ultravioletevisible
(UVevis) spectra were recorded on a Shimadzu UV-2550 UVe
visible spectrophotometer using a quartz cuvette with a 1 cm path
length. Low-resolution MS was obtained using EI ionizations.
Melting points were measured with micro melting point apparatus.
CDCl3)
d
¼ 7.92e7.90 (m, 2H, AreH), 7.57e7.56 (m,1H, AreH), 7.50e
7.48 (m, 2H, AreH), 4.93e4.92 (t, J ¼ 2.0 Hz, 2H, CpeH), 4.61e4.60
(t, J ¼ 2.0 Hz, 2H, CpeH), 4.23 (s, 5H, CpeH), MS (EI), m/z: 291.0
(Mþ).
2.3.3. 2-Chlorobenzoylferrocene (3b)
Red powder; yield 67.7%, m.p. 99e100 ꢂC. 1H NMR (500 MHz,
2.3. Synthesis
CDCl3)
d
¼ 7.53e7.51 (d, J ¼ 7.5 Hz, 1H, AreH), 7.48e7.46 (d,
J ¼ 8.0 Hz, 1H, AreH), 7.43e7.41 (t, J ¼ 6.5 Hz, 1H, AreH), 7.39e7.36
(t, J ¼ 7.0 Hz, 1H, AreH), 4.775 (s, 2H, CpeH), 4.626 (s, 2H, CpeH),
4.308 (s, 5H, CpeH), MS (EI), m/z: 325.5 (Mþ).
2.3.1. General procedure for syntheses of benzoylferrocene
derivatives
A mixture of 10.0 mmol benzoic acid derivatives 1, 50.0 mL
chloroform,1 to 2 drops of DMF as catalyst, and oxalyl chloride (1.90
g, 15.0 mmol) was stirred at room temperature for 3.0e4.0 h. The
solvent and excess oxalyl chloride were removed by rotary evapo-
ration to produce crude benzoyl chloride derivatives 2.
2.3.4. 3-Chlorobenzoylferrocene (3c)
Red powder; yield 52.4%, m.p. 102e103 ꢂC. 1H NMR (500 MHz,
CDCl3)
d
¼ 7.73 (s, 1H, AreH), 7.65e7.63 (d, J ¼ 7.5 Hz, 1H, AreH),

J. Jia et al. / Dyes and Pigments 104 (2014) 137e145
139
Fig. 2. Optical path of DFWM.
7.52e7.48 (t, J ¼ 9.5 Hz, 1H, AreH), 7.39e7.33 (t, J ¼ 7.0 Hz, 1H, Are
H), 4.80 (s, 2H, CpeH), 4.63 (s, 2H, CpeH), 4.31 (s, 5H, CpeH), MS
(EI), m/z: 325.5 (Mþ).
2.3.7. 3,5-Dimethoxybenzoylferrocene (3f)
Red powder; yield 18.3%, m.p. 84e85 ꢂC. 1H NMR (500 MHz,
CDCl3)
J ¼ 2.0 Hz,1H, AreH), 4.95e4.94 (t, J ¼ 2.0 Hz, 2H, CpeH). 4.61e4.60
(t, J ¼ 2.0 Hz, 2H, CpeH), 4.237 (s, 5H, CpeH), 3.875 (s, 6H, OCH3),
MS (EI), m/z: 351.0 (Mþ).
d
¼ 7.07e7.06 (d, J ¼ 2.5 Hz, 2H, AreH), 6.66e6.65 (t,
2.3.5. 4-Chlorobenzoylferrocene (3d)
Red powder; yield 41.9%, m.p. 122e123 ꢂC. 1H NMR (500 MHz,
CDCl3)
d
¼ 7.87e7.58 (d, J ¼ 8.5 Hz, 2H, AreH), 7.46e7.44 (d,
J ¼ 8.5 Hz, 2H, AreH), 4.88 (t, J ¼ 2.0 Hz, 2H, CpeH), 4.61e4.60 (t,
2.3.8. 2,3,4,5-Tetrafluorobenzoylferrocene (3g)
J ¼ 1.5 Hz, 2H, CpeH), 4.202 (s, 5H, CpeH), MS (EI), m/z: 325.5 (Mþ).
Red powder; yield 21.0%, m.p. 81e83 ꢂC. 1H NMR (500 MHz,
CDCl3),
d
¼ 7.27e7.23 (m, 1H, AreH), 4.819 (s, 2H, CpeH), 4.69e4.68
2.3.6. 2-Methoxybenzoylferrocene (3e)
(t, J ¼ 2.0 Hz, 2H, CpeH), 4.254 (s, 5H, CpeH), MS (EI), m/z: 363.0
Red powder; yield 61.2%, m.p. 138e139 ꢂC. 1H NMR (500 MHz,
(Mþ).
CDCl3)
d
¼ 7.45e7.42 (m, 2H, AreH), 7.03e7.00 (m, 2H, AreH), 4.76
(t, J ¼ 2.0 Hz, 2H, CpeH). 4.55e4.54 (t, J ¼ 2.0 Hz, 2H, CpeH), 4.237
2.3.9. 4-Nitrobenzoylferrocene (3h)
(s, 5H, CpeH), 3.85 (s, 3H, OCH3), MS (EI), m/z: 321.0 (Mþ).
Red powder; yield 10.8%, m.p. 189e190 ꢂC. 1H NMR (500 MHz,
CDCl3)
d
¼ 8.37e8.35 (m, 2H, AreH), 8.31e8.30 (m, 2H, AreH),
4.62e4.61 (t, J ¼ 4.0 Hz, 2H, CpeH), 4.292 (s, 5H, CpeH), 4.07e4.06
(t, J ¼ 4.0 Hz, 2H, CpeH), MS (EI), m/z: 336.1 (Mþ).
Fig. 3. The photo of phase-conjugated beam and input beam.
Fig. 4. The UVevis spectrum of 3ae3l in DMF.

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J. Jia et al. / Dyes and Pigments 104 (2014) 137e145
Fig. 5. DFWM signal versus delay time for 3ae3l in DMF solution.

J. Jia et al. / Dyes and Pigments 104 (2014) 137e145
141
Table 1
2H, AreH), 4.77 (s, 2H, CpeH), 4.45 (s, 2H, CpeH), 4.23 (s, 5H, Cpe
H), 3.86 (s, 3H, OCH3), MS (EI), m/z: 321.0 (Mþ).
The values of c(3)
,
g
, n2, and the respond times for 3ae3l.
c(3)
n2
Compound
I
n
g
Response
(10ꢁ13 esu) (10ꢁ12 esu) (10ꢁ31 esu) time
s(fs)
2.3.12. 4-Fluorobenzoylferrocene (3k)
Red powder; yield 46.2%, m.p. 114e116 ꢂC. 1H NMR (500 MHz,
3a
3b
3c
3d
3e
3f
3g
3h
3i
2.51656 1.4309 3.857
2.2077 1.4300 3.608
2.18091 1.4306 3.589
2.30618 1.4303 3.689
1.9277 1.4306 3.374
1.59033 1.4307 3.065
4.83337 1.4302 5.340
10.46603 1.4303 7.859
3.18123 1.4304 4.333
2.34178 1.4310 3.721
3.69335 1.4308 4.672
3.17254 1.4303 4.327
7.098
6.648
6.607
6.795
6.212
5.642
9.836
14.475
7.980
6.847
8.599
7.969
1.281
1.199
1.192
1.226
1.121
1.018
1.774
2.611
1.440
1.236
1.552
1.437
55.64
51.15
51.15
54.20
56.56
50.84
66.10
69.42
65.59
49.71
68.64
63.03
CDCl3)
d
¼ 8.47e8.34 (d, J ¼ 7.5 Hz, 2H, AreH), 7.16 (d, J ¼ 7.0 Hz, 2H,
AreH), 4.76e4.78 (m, 2H, CpeH), 4.42 (s, 2H, CpeH), 4.25 (s, 5H,
CpeH), MS (EI), m/z: 309.0 (Mþ).
2.3.13. 4-Bromobenzoylferrocene (3l)
Red powder; yield 39.7%, m.p. 117e119 ꢂC. 1H NMR (500 MHz,
CDCl3)
d
¼ 8.25e8.08 (d, J ¼ 8.5 Hz, 2H, AreH), 7.89 (d, J ¼ 7.5 Hz,
3j
3k
3l
2H, AreH), 4.77 (S, 2H, CpeH), 4.45 (s, 2H, CpeH), 4.23 (s, 5H, Cpe
H), MS (EI), m/z: 369.9 (Mþ).
2.4. Nonlinear optical measurements
2.3.10. 4-Methylbenzoylferrocene (3i)
Red powder; yield 42.1%, m.p. 129e130 ꢂC. 1H NMR (500 MHz,
CDCl3)
H), 4.80 (s, 2H, CpeH), 4.54e4.42 (s, 2H, CpeH), 4.24 (s, 5H, CpeH),
2.36 (s, 3H, CH3), MS (EI), m/z: 305.0 (Mþ).
The third-order NLO properties were measured by DFWM with
the 80 fs laser pluses (800 nm) generated by a Ti: sapphire laser
with repetition rate of 1 kHz. The experiments were performed at
22 ꢂC in DMF solutions using a 1 mm-thick quartz cell. As a refer-
ence, the optical nonlinearity of the standard sample (CS2) was also
observed.
d
¼ 8.17 (d, J ¼ 8.0 Hz, 2H, AreH), 8.06 (d, J ¼ 8.5 Hz, 2H, Are
2.3.11. 4-Methoxybenzoylferrocene (3j)
Red powder; yield 63.8%, m.p. 125e126 ꢂC. 1H NMR (500 MHz,
The input beam was split into two beams (k1 and k2) of nearly
equal energies using a beam splitter. The input beam, k2, passed
CDCl3)
d
¼ 8.25e8.08 (d, J ¼ 8.0 Hz, 2H, AreH), 7.89 (d, J ¼ 7.0 Hz,
Fig. 6. The geometries optimized by B3LYP/6-31G(d) level.

142
J. Jia et al. / Dyes and Pigments 104 (2014) 137e145
Table 2
Parts of bond length (in A) and the dihedral angle (in ꢂ) in isomers at B3LYP/6-31G(d)
level. The number of C is shown in Fig 7.
ꢀ
Compound
C1eC2
C1eC3
C1eO
:C1eC2eC6eC7
:C1eC3eC4eC5
3a
3b
3c
3d
3e
3f
3g
3h
3i
1.485
1.479
1.483
1.483
1.481
1.485
1.475
1.479
1.486
1.487
1.485
1.483
1.501
1.511
1.504
1.502
1.506
1.504
1.512
1.507
1.499
1.494
1.499
1.501
1.229
1.223
1.228
1.228
1.228
1.228
1.227
1.227
1.229
1.230
1.229
1.229
174.4
174.4
174.8
174.3
173.5
173.7
173.5
174.3
174.1
174.2
174.3
173.9
176.7
175.7
176.8
176.6
176.6
177.0
175.6
176.3
176.7
177.0
176.6
176.7
3j
3k
3l
Fig. 8. The energies of the frontier molecular orbitals in the eight isomers at the
B3LYP/6-31G(d) level.
3. Results and discussion
Among the 12 benzoylferrocene derivatives, 3f and 3g are new
compounds. The compounds were synthesized by the Friedele
Crafts reaction from benzenecarbonyl chloride derivatives and
ferrocene, as illustrated in Fig. 1.
The linear UVevis absorption spectra of the 12 benzoylferrocene
derivatives in DMF solutions are shown in Fig. 4. These compounds
exhibited absorption peaks between 250 and 800 nm. The laser
wavelength (800 nm) used in the DFWM experiment was far from
their resonant bands. Thus, the third-order NLO susceptibilities c(3)
of the compounds were off-resonant nonlinear responses.
The third-order NLO susceptibility, c(3)
, is calculated by
comparing the measured signal for the sample with that for CS2
under the same experimental condition. The c(3) is obtained ac-
cording to the following formula [28]:
Fig. 7. The structure schematic of carbonyl-type ferrocene. The numbers are construed
respectively as the carbon atoms.
ꢀ ꢁ
ꢀ
ꢁ
IS 1=2Lr ns 2 aL expð
a
L=2Þ
cðs3Þ
¼
cðr3Þ
through a delay line driven by a stepping motor so that the optical
path length difference between the k2 and k1 beams could be
adjusted during the measurement. The angle between the beams
was about 5ꢂ. When the beams were overlapped spatially in the
sample, the generated signal beam (the phase-conjugated beam
k3) passed through an aperture, which was recorded by a photo-
diode, and then analyzed by a lock-in amplifier and computer (as
shown in Figs. 2 and 3).
a
Þ
Ir
Ls nr 1 ꢁ expðꢁ L
where I is the intensity of the phase-conjugated beam, L is the
sample path length, n is the linear refractive index, and is the
a
linear absorption coefficient. The subscripts ‘s’ and ‘r’ refer to the
sample and CS2, respectively. The values of c(r3) and nr for CS2 are
6.7 ꢀ 10ꢁ14 esu and 1.632, respectively [29e31].
The temporal response of the phase conjugate signal as a
function of the delay time of the input beam is shown in Fig. 5. The
response times of the samples could be obtained from this function.
2.5. Calculated method
The values of
c g and response times for the samples
(3), n2,
The ground-state geometry of all isomers was optimized at the
B3LYP level [25]. And the basis set of 6-31G (d) was used to opti-
mize the geometries. Then the vibrational frequencies were
calculated at the B3LYP/6-31G (d) level. The optimized geometries
were locating at the local lowest point on the potential energy
surface because that all the predicated vibrational spectra had no
imaginary frequency [26]. Then the MOs and natural charge ana-
lyses at the same level of theory were carried out for some isomers.
All the calculations were performed within the Gaussian 09
quantum chemical package [27].
deduced and calculated from the experimental results are listed in
Table 1.
The benzoylferrocene derivatives 3ae3l possess a highly delo-
calized
p-conjugated electron system. The g values of the ben-
zoylferrocene derivatives are higher than that of the other third-
order NLO materials, such as organobimetallic Ru(II)eRe(I) 4-
ethynylpyridyl complexes [32], which is about 6 ꢀ 10ꢁ34 esu, and
are also higher than that of ferrocene, which is 1.6 ꢀ 10ꢁ35 esu [33].
The fully optimized geometries of the twelve compounds were
shown in Fig. 6. The atoms of cyclopentadiene ring (Cp) and the
benzene ring (Ph) are all at the plane, respectively. The C of the
Table 3
The energy (in eV) of the HOMO, LUMO, and HOMO-LUMO gap (EHOMO, ELUMO, Egap in
eV) of compounds 3a, 3b, 3e, 3h, and 3i calculated at the B3LYP/6-31G(d) level.
Table 4
The Natural charge of some atoms in the compounds 3a, 3b, 3e, 3h, and 3i calculated
at the B3LYP/6-31G(d) level. (Unit: e).
Compound
EHOMO
ELUMO
Egap
3a
3b
3c
3d
3e
ꢁ1.500
ꢁ1.474
ꢁ1.236
ꢁ2.770
ꢁ1.412
ꢁ5.431
ꢁ5.507
ꢁ5.303
ꢁ5.756
ꢁ5.414
3.930
4.033
4.067
2.986
4.002
3a
3b
3e
0.012
0.009
ꢁ0.195
3h
0.031
0.004
ꢁ0.246
3i
0.006
Fe_2Cp
CO
R0
0.006
0.023
0.026
0.009
ꢁ0.004
ꢁ0.009
0.238(dui)
0.039

J. Jia et al. / Dyes and Pigments 104 (2014) 137e145
143
Fig. 9. The charge differential density of the 3a, 3b, 3e, 3h, and 3i.
carbonyl group is almost on the Cp plane with the smallest dihedral
angle (173.5ꢂ) in the compound 3e and 3g as shown in Table 2. At
the same time, the C of the carbonyl group is almost on the Ph plane
with the smallest dihedral angle (175.6ꢂ) in the 3g as shown in
Table 2. The dihedral angle formed by the Cp and Ph is about 45ꢂ in
all the twelve complexes. And the ferrocene almost unchange the
symmetry of D2d in the 12 complexes. The substitutions of eNO2, e
Cl, and e4F shorten the bond lengths of the C1 and C2 (The number
Fig. 10. The frontier molecular orbitals of the 3a, 3b, 3e, 3h, and 3i.

144
J. Jia et al. / Dyes and Pigments 104 (2014) 137e145
of C is shown in Fig 7) and the bond length of C1eC3 as shown in
Table 3. The electron-withdrawing eNO2 decreases the energy of
HOMO and HOMO-LUMO gap obviously as shown in Table 3 and Fig
8. The lower energy of LUMO illustrates the electron injection was
improved. The lower Egap illustrates these compounds with
electron-withdrawing substitutional aryl would have larger three-
order NLO which accord with the above experiment as well.
These derivatives contain electron-withdrawing substituents
aryl radical groups and electron-donating ferrocenyl in the form of
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lated listed in Table 4. Electron-withdrawing substituents such as
the eNO2 in 3h has higher natural charge values (ꢁ0.246 e) than
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with the
g values of these compounds in experiment from Table 4.
The net charge of eNO2 in 3h with ꢁ0.246 is much lower than that
of eCH3 with 0.039 in 3i. The charge differential density (shown in
Fig 9) of these five compounds also shown that the eNO2 has larger
effect on the charge density in the 3h than other compounds.
Therefore, the charge transfer to eNO2 is more than others ac-
cording with the result from the natural charge. The stronger is the
electron-withdrawing ability of the substituents of the aryl groups,
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the higher are the
g values.
The frontier molecular orbitals (FMOs) of 3a, 3b, 3e, 3h, and 3i
compounds are listed in Fig. 10. The FMOs (LUMOþ2, LUMOþ1,
LUMO, HOMO, HOMOꢁ1, and HOMOꢁ2) of the five calculated
isomers are similar to each other in principal character. The elec-
tronic density of HOMOꢁ1 mainly located on the ferrocene, espe-
cially the d atomic orbital (AO) of Fe atom. The HOMO is similar to
the HOMOꢁ1 in every compound. It is worthwhile to refer to that
the p AOs of C and O of the eCOe bridges had some contributions to
the LUMO en the five compounds. The electronic density of LUMO is
mainly composed by the d AO of Fe, the eCOe, and the Ph in the 3a,
3b, 3e, and 3i. Different with these compounds, the d AO of Fe has
small contribution to LUMO in 3h. This is maybe the main reason
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derivatives possessing DepeA structures. The third-order NLO
properties in the femtosecond range were investigated using the
DFWM technique at 800 nm. The third-order NLO susceptibilities of
the compounds were 3.065e7.859 ꢀ 10ꢁ13 esu. The second-order
hyperpolarizabilities
of
the
molecules
were
1.018e
2.611 ꢀ 10ꢁ31 esu. These compounds possess ultrafast response
times of <70 fs. The DFT study showed that the third-order NLO
properties were increased with the increasing electron-
withdrawing ability in accordance with the decreasing Egap. With
the increasing ability of attract electron, the transferred charge to
the substituent is increasing, especially in the 3h. And the affection
on the electronic reallocate is increasing with the increasing
electron-withdrawing ability.
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We are very grateful to Dr. Shian Zhang from the Key Laboratory
of Optical and Magnetic Resonance Spectroscopy in East China
Normal University, for the DFWM experiment and the helpful
discussion. This research was financially supported by the National
Natural Science Fund of China (Grant no. 20876148).
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